1. Field of the Invention
This invention relates to a catalytic method for the conjoint preparation of N-aminoethylpiperazine and tetraethylenepentamine. More particularly, this invention relates to a catalytic method for the conjoint manufacture of N-aminoethylpiperazine and tetraethylenepentamine from ethylenediamine and diethanolamine. Still more particularly, this invention is directed to the use of a titania catalyst to which a minor amount of phosphorus has been thermally chemically bonded at the surface thereof in the form of phosphate linkages for the conjoint manufacture of N-aminoethylpiperazine and tetraethylenepentamine by passing ethylenediamine and diethanolamine over a catalyst composed of titania to which a minor amount of phosphorus (0.5 to 7 wt. %) has been thermally chemically bonded in the form of phosphate linkages.
2. Prior Art
The catalysts used in the practice of the process of the present invention are disclosed in Vanderpool European patent application Ser. No. 83,307,520.3 published Aug. 28, 1984, wherein they are disclosed as useful in promoting the reaction of ethylenediamine with ethanolamine to provide essentially linear polyethylenepolyamine reaction products. Minor quantities of cyclic products are also formed.
Ford U.S. Pat. No. 4,316,841 discloses a process for reforming polyalkylene polyamines, preferably to non-cyclic polyalkylene polyamines, using as the catalyst a phosphate of a Group IA or Group IIA, preferably boron phosphate. European patent application No. 151,232 is directed to a process for converting piperazine to ethylenediamine and N-aminoethylpiperazine by reductively aminating piperazine a reductive amination catalyst such as a metal or oxide of copper, nickel, cobalt, palladium, rhodium, etc.
The preparation of N-aminoethylpiperazine by the hydrogenation of nitrileacetonitrile using a hydrogenation catalyst, such as a nickel, copper, iron, palladium, cobalt, chromium, rhodium, molybdenum or titanium catalyst is disclosed in Yeakey U.S. Pat. No. 3,733,525. McConnel U.S. Pat. No. 4,324,917 is directed to the use of a phosphorus-containing cation exchange resin to promote the reaction of an alkanolamine with an alkyleneamine to provide predominantly non-cyclic polyalkylene polyamine reaction products. In Brennan et al. U.S. Pat. No. 4,049,657 a process is disclosed for selectively preparing N-aminoethylpiperazine by cycling a primary or secondary amino alkanol in the presence of a catalytically effective amount of a phosphorus compound such as an acidic metal phosphate, a compound of phosphoric or phosphorous acid, an alkyl or aryl phosphate or phosphite, etc. European patent application No. 0,138,050 discloses a process for preparing polyalkylene polyamines by reacting an alkanolamine with ammonia or a primary or secondary amine in the presence of a Group IIIB metal acid phosphate, such as a phosphate, monohydrogen phosphate or dihydrogen phosphate (e.g., a lanthanium, praseodymium or neodymium phosphate).